CN1125846C - Light-converting material and composition for producing same - Google Patents
Light-converting material and composition for producing same Download PDFInfo
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- CN1125846C CN1125846C CN 97182495 CN97182495A CN1125846C CN 1125846 C CN1125846 C CN 1125846C CN 97182495 CN97182495 CN 97182495 CN 97182495 A CN97182495 A CN 97182495A CN 1125846 C CN1125846 C CN 1125846C
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Abstract
The present invention relates to material comprising ground masses, apatite and at least one europium composite compound whose general formula is Mex<m>Euy<3>Rz<n>, wherein mx+3y = nz, Mex <m> = Mex', <m'>+Mex'<m'>+..., Rz' <n> = Rz'<n'> +Rz'<n'>+..., mx = m'z'+m'x'+..., nz = nZ'+n'z'+..., x>= 1, and 0>=y>=0.01. Me refers to gadolinium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, aluminum, bismuth, tin, titanium, manganese, calcium, barium, zinc, cadmium, sodium, potassium, rubidium and cesium, R refers to oxygen, sulfur, fluorine, bromine, phosphorus, boron, vanadium, molybdenum, tungsten, germanium and compounds thereof, and m and n respectively refer to the charge of Me or R ions. The compositions for producing the material comprise the following components, in the proportion by weight, 0.01 to 10.0 of apatite, 0.01 to 10.0 of composite compound and the balance of ground mass forming agents, such as polymer, fiber and compositions generated by glass or substances generated by varnish and adhesive.
Description
Invention field
The present invention relates to matrix material, relate to the light-converting material that is used for agricultural, medicine, biotechnology and optics industry particularly.
Background of invention
An object of the present invention is to provide a kind of light-converting material that UV-light can be converted to ruddiness and can keep this ability for a long time.
It is urgent especially that the problems referred to above become; at first be because protection is human, animal and plant is not subjected to solar ultraviolet radiation and technology ultraviolet radiation; as what known, ultraviolet radiation can cause the sun to skin burn and the skin melanoma in the development of tumor disease.Secondly, many document descriptions the advantageous effects of ruddiness, it strengthens catalase, enzymic activity (the Y.A.Vladimirov etc. that surpass oxide compound dismutase and glutathione reductase, " free radical biomedicine ", the 5th phase, 1988, the 281-286 page or leaf), ruddiness itself has reduced the quantity of destroying cell activity form oxygen again, also strengthens DNA and proteinic synthetic (T.I.Karu " photobiology of low energy laser treatment " simultaneously, in " laser science and technology " such as V.S.Letokhov, breathe out Wood Science Press, Ku Er, Switzerland, 1989), the ruddiness skin rehabilitation that promotes wound healing again and the sun is burnt itself.In addition, the ruddiness width of cloth is penetrated (wavelength 600-630 nanometer) and can be absorbed by the chlorophyll-b of greenery most effectively.Therefore, the light compositing process is faster, and the green weight of plant increases, and the output of greenhouse cultivation industry increases and the ripening stage shortens (Stoy V., plant physiology, 1955, the 8 volumes, 963-986 page or leaf); InadaK., plant and stechiology, 1976, the 17 volumes, 355-365 page or leaf; GB2158833).
(US 4081300 to contain a kind of matrix and a kind of energy ultraviolet radiation-absorbing; JP53-136050; JP A3-158103 (announcement on July 8th, 1991); FR2419955) it is known maybe providing the material of the active additive of proportional ultraviolet ray emission (WO94/17135).As a kind of active additive, this material comprises carbon black and phthalocyanine pigment (JP53-136050); Benzophenone or benzotriazole (FR2419955); The positive tertiary butyl of Whitfield's ointment (phenyl) ester or 2-hydroxyl-4-methoxy benzophenone (JPA3-158103); The combination of the dyestuff of the compound of Whitfield's ointment, citric acid and oxalic acid and cyan or purple (WO 94/17135).Matrix is extruded into thermoplastic polymer film (US 4081300, JP53-136050, FR 2419955), or make (JPA3-158103) by filamentary material (natural or synthetic), or make tabular thermoplastic polymer (WO 94/17135), or make (WO 94/1735) by non-filamentary material, line or varnish.The film like material is used for agricultural mostly, with protection greenhouse (US4081300, JP 53-136050, FR 2419955).The textile-like material is used to make roof hood and cool fluffy (JP A3-158103), and board-like material is used to produce roof hood, cool fluffy even roof top layer (WO94/17135).
Yet all these materials all can not convert ultraviolet ray to ruddiness.
Containing the coordination compound of a kind of matrix and at least a rare earth metal (europium, samarium, terbium, gadolinium) is known as the light-converting material (CH 667463, GB 2158833) of active additive, and it makes the ultraviolet component in the light convert orange-red light spectral limit (580-750 nanometer) to.Matrix is extruded into thermoplastic polymer film.The composition of producing this material contains the component of active additive of 0.001-5.0% (weight) and 95.0-99.99% (weight) formation matrix.Said composition contains at least a polymkeric substance and forms component as matrix, and it is selected from polyethylene, polypropylene, polyvinyl chloride, polycarbonate (PC), polystyrene, polymethylmethacrylate or their multipolymer.Simultaneously, this material only is being not more than its light conversion activity of maintenance in 60 days.Because be used to produce the coordination compound of alkene earth metal compound under light action, decomposing rapidly of this material.
Contain a kind of matrix and at least a general formula is [(La
1-xEu
x) O]
m(Lig)
nComplex chemical compound be known as the light-converting material (RU 2059999) of active additive, wherein Lig is F, Cl, Br, O, S, Se, this material also can convert the ultraviolet component in the light to orange red spectrum (580-750 nanometer).This material is made thermoplastic polymer film.The composition of producing this material contains active additive of 0.05-1.0% (weight) and 99.0-99.95% (weight) matrix generation agent.Said composition contains and at least aly is selected from the multipolymer of polyethylene, ethene and vinyl acetate between to for plastic (EVA) or the polymkeric substance of polyethylene terephthalate generates agent as matrix.
This material also can convert the ultraviolet component in the light source light spectrum to ruddiness.But, this material only kept its activity in 300 days, because the oxo halogenide of all rare earth compounds, particularly oxidation selenide particularly will decompose in steam in air.
Summary of the invention
Main purpose of the present invention is that the ability by the anti-light of enhanced activity additive, air and steam effect prolongs the ability that light-converting material converts UV-light to ruddiness under identical conversion intensity.
Another purpose is to enlarge the suitable scope of making the material of the material with light transfer capability.
Another purpose is to improve the hot protective capability of material.
Above-mentioned purpose of the present invention contains a kind of matrix and a kind of light-converting material that converts UV-light the active additive of orange-red light spectral limit to reaches by providing a kind of.According to the present invention, as the photolytic activity additive, this material contains phosphatic rock and at least a formula M e
x mEu
y 3R
z nEuropium (III) complex chemical compound or the mixture of the complex chemical compound of samarium (III), terbium (III) or the gadolinium (III) of this compound and at least a following general formula:
Me
x mM
y 3R
z nIn the formula, mx+3y=nz, Me
x m=Me
X ' M '+ Me
X " M "+ ..., R
z n=R
Z ' N '+ R
Z " N "+ ..., mx=m ' x '+m " x "+..., nz=n ' z '+n " and z "+..., x 〉=1.0 〉=y 〉=0.01.
Wherein Me is the metal that is selected from yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, aluminium, bismuth, tin, titanium, manganese, calcium, barium, zinc, cadmium, sodium, potassium, rubidium, caesium,
M is the metal that is selected from europium, samarium, terbium, gadolinium,
R is selected from the element of oxygen, sulphur, fluorine, chlorine, bromine, phosphorus, boron, vanadium, molybdenum, tungsten, germanium or their combination,
M and n are respectively Me or R ionic electric charge.
Wherein active additive can be distributed in the matrix or be distributed on the surface of matrix.
This material contains the active additive of at least 0.02% (weight).
This matrix is made printing opacity.
As phosphatic rock, this material includes crystalline structure and is in the formula that always the consists of Ca of finely divided state
10(PO
4)
6R '
2The mixture natural or synthetic phosphatic rock or its any ratio of (wherein R ' is F, Cl or OH).
As complex chemical compound, this material contains at least a complex chemical compound, and wherein nz=3, R are formula Me
xM
yO among the OGal, Gal, Gal are F, Cl, Br; Or nz=6 wherein, R is formula Me
xM
yO
2Hal or formula Me
xM
yO
2S
1 ± 0.2In O, Hal, Hal is S or Se; Or nz=6 wherein, R is or Me
xM
y(VO
4)
2In VO
4Or wherein R is formula Me
xM
y(BO
3)
Z 'In (PO
4)
Z "BO
3, PO
4Or wherein R is formula Me
xM
y(VO
4)
Z '(PO
4)
Z "In VO
4, PO
4Formula wherein R is formula Me
xM
y(VO
4)
Z '(PO
4)
Z "(BO
3)
Z In VO
4, PO
4, BO
3Wherein R is formula Me
xM
y(BO
2)
Z '(WO
4)
Z ', formula Me
xM
y(BO
2)
Z '(MoO
4)
Z 'In BO
2, WO
4, MoO
4Or the mixture of these compounds.
As formula M e
xM
yOGal or Me
xM
yO
2The compound of Hal, this material contain the product of the solid solution of the oxide compound of handling Me and M in alkaline halide or chalcogenide medium under 800-1200 ℃; As formula M e
xM
yO
2S
1 ± 0.2Compound, this material contains in the sulphur medium products of handling the oxide compound of Me and M down at 1200 ℃; As formula M e
xM
y(VO
4)
2Compound, this material contains the oxide compound of Me and Me and ammonium vanadate at the 900-1100 ℃ of interactional product of following solid phase; As formula M e
xM
y(BO
3)
Z '(PO
4)
Z "Compound, this material contains the oxide compound of Me and M and boric acid and ammonium phosphate at the 900-1100 ℃ of interactional product of following solid phase; As formula M e
xM
y(VO
4)
Z '(PO
4)
Z "Compound, this material contains the metal oxide of Me and M and vanadate and ammonium phosphate at the 1000-1200 ℃ of interactional product of following solid phase; As formula M e
xM
y(VO
4)
Z '(PO
4)
Z "(BO
3)
Z "Compound, this material contains the oxide compound of Me and M and vanadate and ammonium phosphate and boric acid at the 8O0-1100 ℃ of interactional product of following solid phase; As formula M e
xM
y(BO
2)
Z '(WO
4)
Z "Or Me
xM
y(BO
2)
Z '(MoO
4)
Z "Compound, this material contains the oxide compound of Me and M, tungsten (molybdenum) and boric acid are at the 1100-1200 ℃ of interactional product of following solid phase.
In addition, this material also can contain the coordination compound of at least a metal E, and it is selected from [E (TTA)
3(Phen)], [E (TTA)
3(TPhPO)
2], (DPhG) H[E (TTA)
4], (DPhG) H[E (HFAA)
4], [E (HFAA)
3(Phen)], [E (HFAA)
3(TPhPO)
2], (DPhG) H[E
4(AA)
4], [E (AA)
3(Phen)], [E (BB)
3(Phen)], [E (TFA)
3(Phen)], (DPhG) H[E (TFA)
4], [E (Capr)
3(Phen)], [E
2(Ter)
3(Phen)
2], [E (NO
3)
3(Phen)
2],
E is the metal that is selected from europium, samarium, terbium, gadolinium;
H is a hydrogen ion; TTA closes negatively charged ion for the thenoyltrifluoroacetone acid group; HFAA closes negatively charged ion for the hexafluoro acetylacetonate, and BB closes negatively charged ion for the benzoyl benzoate anion; AA is that acetylacetonate closes negatively charged ion; TFA closes negatively charged ion for the trifluoroacetic acid root, and Capr closes negatively charged ion for the caproic acid root; Ter closes negatively charged ion for terephthaldehyde's acid group; Phen is 1, the 10-phenanthroline; TPHPO is a triphenylphosphine oxide; DPhG is a vulkacit D.
Coordination compound as metal E; this material contains the nitrate of europium (III), samarium (III), terbium (III) or gadolinium (III) by thenoyltrifluoroacetone or hexafluoro Acetyl Acetone or Acetyl Acetone or benzoyl phenylformic acid or trifluoroacetic acid, caprone acid or terephthalic acid and 1; the 10-phenanthroline; or triphenylphosphine oxide, or the product of vulkacit D processing under 80-90 ℃ in water alcohol medium.
This material can contain a kind of film, plate or cloth form, matrix of woven or non-woven fabrics/filamentary material made.
Matrix can be made by thermoplastic polymer.
Matrix can be made by soluble polymer.
Matrix can be got by the polyester that is selected from polymethylmethacrylate, poly-n-butyl methacrylate, polycarbonate (PC), polyethylene terephthalate and derivative thereof, or make by the polyolefine that is selected from polypropylene, polyvinyl chloride, polystyrene, polyethylene and derivative thereof, make by multipolymer or these mixture of polymers of polymeric amide or derivatives thereof or these polymkeric substance.
Matrix can (be comprised the natural fiber of cotton, silk, wool, hemp and composition thereof or comprise that the synthon of viscose glue, acetic ester, caprone, nylon, polymeric amide, polyester and multipolymer thereof, mixture or blend or the mixture of these filamentary materials make by filamentary material.
Matrix can be made by the silicate glass of silicate glass or modification.
Matrix can be made by synthetic glass.
In addition, material also can contain varnish or tackiness agent.
As varnish or tackiness agent, this material can contain silicone, polyester, polyepoxide, Resins, epoxy or its mixture.
Described these purposes are also by providing the composition of producing the light-converting material that contains matrix generation agent and active additive to reach.As active additive, said composition contains phosphatic rock and at least a formula M e
x mM
y 3R
z nEuropium (III) complex chemical compound or this complex chemical compound and at least a formula M e
x mM
y 3R
z nThe mixture of complex chemical compound of samarium (III), terbium (III) or gadolinium (III), in the formula, mx+3y=nz, Me
x m=Me
X ' M '+ Me
X " M "+ ..., R
z n=R
Z ' N '+ R
Z ' N "+ ..., mx=m ' x '+m " x "+..., nz=n ' z; + n "
Z "+ ..., X 〉=1.0 〉=Y 〉=0.01,
Wherein, Me is the metal that is selected from yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, aluminium, bismuth, tin, titanium, manganese, calcium, barium, zinc, cadmium, sodium, potassium, rubidium, palladium;
M is the metal that is selected from europium, samarium, terbium, gadolinium;
R is element or its compound that is selected from oxygen, sulphur, fluorine, chlorine, bromine, phosphorus, boron, vanadium, molybdenum, tungsten, germanium.
M and n are respectively the electric charge of Me or R.
Generate agent as matrix, said composition contains thermoplastic or polymer soluble, or filamentary material (natural, synthetic or blended) or composition or varnish/tackiness agent of producing the silicate glass of synthetic glass, silicate glass or modification generate material, and each component has following ratio (% (weight)):
Phosphatic rock 0.01-10.0
Complex chemical compound 0.01-10.0
Matrix generates the agent remainder
In addition, said composition also can contain the coordination compound of at least a metal E, and it is selected from
[E (TTA)
3(Phen)], [E (TTA)
3(TPhPO)
2], (DPhG) H[E (TTA)
4], (DPhG) H[E (HFAA)
4], [E (HFAA)
3(Phen)], [E (HFAA)
3(TPhPO)
2], (DPhG) H[E
4(AA)
4] [E (AA)
3(Phen)], [E (BB)
3(Phen)], [E (TFA)
3(Phen)], (DPhG) H[E (TFA)
4], [E (Capr)
3(Phen)], [E
2(Ter)
3(Phen)
2], [E (NO
3)
3(Phen)
2], each component has following ratio (% (weight))
Phosphatic rock 0.01-10.0
Complex chemical compound 0.01-10.0
Coordination compound 0.01-10.0
Matrix generates the agent remainder
Generate agent as matrix, said composition can contain and is selected from polymethylmethacrylate, poly-n-butyl methacrylate, polycarbonate (PC), polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene, polyethylene, the polymkeric substance of polymeric amide, the derivative of these polymkeric substance, the multipolymer of these polymkeric substance or these mixture of polymers.
Generate agent as matrix, said composition also can contain the composition of producing silicate glass or modified Portland glass.
Generate agent as varnish/tackiness agent, said composition can contain silicone, polyester, polyepoxide, Resins, epoxy or its mixture.
As natural fiber material, said composition can contain and is selected from silk, wool, cotton, big harl or its mixture.
As composite fibre materials, said composition can contain fiber or its mixture that is selected from viscose glue, acetic ester, polyester, polymeric amide, polyacrylamide.
In order to understand fully spirit of the present invention, we the alkene earth metals twinkler complex chemical compound of following general formula as additive and be included in the material that provides:
Me
x mM
y 3R
z nIn the formula, mx+3y=nz, Me
x m=Me
X ' M '+ Me
X " M "+ ..., R
z n=R
Z ' N '+ R
Z " N "+ ..., mx=m ' x '+m " x "+..., nz=n ' z '+n " z "+..., x 〉=1.0 〉=y 〉=0.01.M and n are respectively Me or R ionic electric charge.
This formula reflects the structure of the complex chemical compound of the anionicsite R that contains ion activation agent Me, luminescence center ion M and compound, and R offsets the positive charge of Me and M, and wherein m and n are respectively Me and R ionic electric charge.
Must point out that be assorted polynuclear complex as the complex chemical compound of active additive, wherein ion activation agent Me and luminescence center M connect each other by abutment R.The latter produces the notion of " solid solution ", because in solid solution, the generation of assorted polynuclear compounds is most probable.
As (the E.F.Kustor that has found, G.A.Bandarkin, E.N.Muravyov, V.P.0rlovsky, " electronic spectrum of rare earth compounds " I.V.Tananayev edits science, Moscow, 1981, the 183 pages), the assorted polynuclear compounds that contains europium (III) provides the brightest fluorescence (keeping the most important scope of luminescence emissions in red range) in the 610-630 nanometer range.So the molecular formula of describing the compound element structure comprises two class atom Me and M at least as active additive, its index is x and y, restriction numerical value x 〉=1.0 〉=y 〉=0.01, and wherein M is at least Eu (III).
For solving the prior art problem, the prerequisite of complex chemical compound suitability is the existence of europium (III) ion in compound.The compound of samarium (III), terbium (III), gadolinium (III) plays a secondary role.
The scope of numerical value x and y is by minimum value y=0.01 decision because when the content of luminescence center M hour, ultraviolet conversion is a demulcent; Drawn by experience, numerical value x=1.0 is a maximum value.
Shown in molecular formula in, the anionicsite of complex chemical compound and numerical value R
Z "Combine, may comprise different structure and negatively charged ion different ratios: R
Z '+ R
Z "+ R
Z + ..., z=z '+z wherein "+z +...
The structure of the complex chemical compound twinkler of known vanadic acid Gadolinium phosphate-europium for example, is described with following formula:
Y
xEu
y(PO
4) (VO
4) in the formula, Me is Y
x 3, M is Eu
y 3, R=(PO
4)
1 3-+ (VO
4)
1 3-Nz=1 * 3+1 * 3=6; X=1.9 wherein, mx=3 * 1.9=5.7; Y=0.1 wherein, 3y=3 * 0.1=0.3, so mx+3y=5.7+0.3=6 and mx+3y=nz.
This feelings also with formula Ba (Gd)
1.9Eu
0.1(WO
4)
4Compound identical, Me wherein
x m=Me
X ' M '+ Me
X " M "=Ba
1 2+ Gd
1.9 3, M
y=Eu
0.1 3, R=(WO
4)
4 2-Z=4, n=2, nz=4 * 2=8; X '=1 wherein, x "=1.9, m '=1.0, m "=3.0, mx=m ' x '+m " x "=2 * 1+3 * 1.9=2+5.7=7.7; Y=0.1 wherein, so 3y=3 * 0.1=0.3, so mx+3y=7.7+0.3=8.0 are mx+3y=nz.
It seems that the molecular formula of the assorted multinuclear complex chemical compound that therefore, is proposed be the molecular formula of describing complex chemical compound (twinkler) structure in those structures of our technological achievement of selecting to reach us the most fully.
As what find with experiment; phosphatic rock (natural or synthetic; mean particle size is the 4-5 micron) can keep being contained in the luminous power of the complex chemical compound in the light-converting material structure on the one hand for a long time as active additive; can strengthen the hot protection feature of this material on the other hand, thereby strengthen this material and prolong its duration of service.
In addition, we also disclose, and the combination of phosphatic rock and complex chemical compound promotes the high transmit power at green and cyan light spectral limit.
Employed compound (assorted multinuclear) compound that makes europium (III), samarium (III), terbium (III) and gadolinium (III) with the solid phase high-temperature synthesis is a quite stable.Combining with natural or synthetic phosphatic rock makes these compounds be fit to be included in the structure of high molten organic polymer, for example polyethylene terephthalate or polycarbonate (PC).
The coordination compound of europium (III), samarium (III), terbium (III), gadolinium (III) is as the additional component of active additive, because they play bright luminous effect in green and orange red spectral range, they are dissolved in the polymkeric substance (except nitrate and terephthalate); Owing at first absorb the ultraviolet component of sunlight, they prolong the effect of complex chemical compound twinkler.
Necessary and the sufficient content of the coordination compound of phosphatic rock, complex chemical compound and rare earth element in the material of selecting to be proposed with experimental technique.Discovery content of phosphatic rock and every kind of additive of complex compound in this material is invalid less than 0.01% (weight), because can not reach technical result.It is above with the absorption increase of sunlight ray in this material that the concentration increase of every kind of additive reaches 10.0% (weight), when if this material is printing opacity, can not keep under the situation of light transfer capability the transparency variation of material, active additive luxus consumption for a long time at material.The combination of described characteristic is achieved described purpose, and the light protective capability that promptly makes this material convert UV-light to ruddiness under ultraviolet ray converts the same intensity of red color spectrum range to prolongs and the heat reflection character enhancing of material.
Must point out, the material that proposes in order to produce, the selection that matrix generates agent influences the range of application of the product that this material makes.For example, if this material is intended for use the greenhouse overcoat, obviously matrix should be the film of printing opacity.Here, any known thermoplasticity or solubility film-forming polymer all can be used as matrix and generate agent, for example polymethylmethacrylate, poly-n-butyl methacrylate, logical carbonic ether (PC), polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene, polyethylene, polymeric amide.Generate agent as matrix; can use thermoplastic polymer to make light-converting material; for example be used to produce biotechnological device; for example microorganism culturing and cell cultures with Petri dish, developmental tube, separate flask, kapillary, and be used to produce winter greenhouse protection, fixedly bathroom and animal room plate.
Plan for example to be used for glass room and office building and greenhouse and animal room or be used to produce glass, automobile, sun visor and cool when fluffy when the material that proposes, generate agent as matrix, but the composition of use silicate (or other) glass.
For example to be used to make roof hood against sunshine and cool fluffy in order making, and to be used to produce the required light conversion fabric cloth of cloth against sunshine, generate agent, can use natural and/or the synthetic fiber as matrix.Use particularly synthetic fiber of synthetical, might prepare light conversion non-woven fabrics, and it is used as protecting materials in agricultural.
The explanation of preferred embodiment
Phosphatic rock (natural or synthetic), europium complex chemical compound and the matrix that is applicable to other application are generated agent be used to produce the material that is proposed.
As natural phosphatic rock, the francolite that the most suitable use is colourless, mean particle size is the 4-5 micron.
The method of making synthetic phosphatic rock is known, and have a detailed description in the literature that (method of producing fluorapatite and hydroxyapatite is by Yu.K.Voron ' ko, A.V.Gorbachov, A.A.Zverev, A.A.Sobol, N.N.Morozov, E.N.Murav ' erv, Sh.A.Niyazov and v.P.Orlovshii are using " Eu
3+The phosphatic rock Ca of ion activation
5(PO
4)
3F and Ca
5(PO
4)
3The Raman scattering of the compound of OH structure and luminescent spectrum ", inorganic materials, 1992; the 28th volume, the 3rd phase, the 442nd page and; V.P.Orlovskii, N.M.Romanova, A.V.Sleblevskii; G.E.Sukhanova by G.V.Rodicheva, " the materialization research of Khibini phosphatic rock and with the comparison of hydroxyapatite ", Russia's inorganic chemistry magazine; 1996, the 41 volumes, the 5th phase; describe in the 728th page, and by V.P.Orlovskii.Zh.A.Ezova, G.V.Rodicheva, E.M.Koval, G.E.Sukhanova " is generating hydroxyapatite CaCl
2(NH
4)
2HPO
4-NH
4OH-H
2The condition of O system (25 ℃) ", Russia's inorganic chemistry magazine, 1992, the 37 volumes, have been described the preparation of hydroxyapatite in the 443rd page at the 4th phase).
Preparation also is known (E.F.Kustov, G.A.Bandarkin, E.N.Muraviov as the method for the complex chemical compound of active additive component, V.P.Orlovsky, " electronic spectrum of rare earth compound ", I.V.Tananayev edits, " science ", Moscow, 1981; " rare earth compounds, silicate, germanate, phosphoric acid salt, arsenate, vanadate ", " rare element chemistry " book series, science, Moscow, 1983).
The method of the coordination compound of preparation europium, samarium, terbium and gadolinium is known, and by L.R.Melby, N.J.Rose, E.Abramson, J.C.Caris is in " synthesizing with luminous of some trivalent group of the lanthanides complex compound ", American Chemical Society's will, 1964, the 86 volumes are described in the 5117th page.
Make (E.F.Kustov, G.A.Bandarkin, E.N.Murav iov as active additive component complex chemical compound with traditional high temperature synthetic method, V.P.Orlovsky, " electronic spectrum of rare earth compounds, I.V.Tananayev edits; " science ", Moscow, 1981).According to this method, the oxide compound of europium (III), samarium (III), terbium (III) or gadolinium (III) mixes with the respective components of the anionicsite (R) that generates compound together with the oxide compound of yttrium (III) (or other relevant metals), and places several hours down at 1100-1200/ ℃.The molten alkynes that makes with this method is then through washing, dry and grind.
Embodiment
The preparation of concrete complex chemical compound-luminescent material is described with following embodiment.
Embodiment 1
100.0 gram lanthanum trioxides, 5.7 gram europium sesquioxides are mixed, be added in the mixture of 37.8 gram vanadate and 48.1 gram ammonium phosphate.The container that mixture is packed into and made by glasscarbon will be obtained, then 1200-1250 ℃ of following roasting 4 hours.Then slowly with container cooling and discharging.Soak molten alkynes with deionized water, be divided into mean particle size and be 4 microns finestructure thing.The structure of complex chemical compound is corresponding to formula La
1.9Eu
0.1(VO
4) (PO
4).
Embodiment 2
90.0 gram yttrium oxide and 10.0 gram europium sesquioxides are mixed, under 95 ℃, mixture is dissolved in the nitric acid.Ammonium oxalate is added in the solution that makes, it is as cold as 25 ℃, separate the uniform mixture of yttrium oxalate and europium with filtration method.
Then, be roasting, preparation contains the mixture of settling, 30.0 gram elementary sulfurs, 100.0 gram yellow soda ash and 2.6 gram lithium fluoride.Mixture is put into the glasscarbon container, then in 1220-1260 ℃ of following roasting 4 hours.Then, container is slowly cooled off discharging.Soak molten alkynes with deionized water, be divided into mean particle size and be 4 microns finestructure thing.The structure of the complex chemical compound that makes is corresponding to formula Y
19Eu
0.1O
2S
1
Embodiment 3
100.0 gram yttrium oxide and 8.25 gram europium sesquioxides are mixed, 109.1 gram ammonium vanadate are added in the mixture.Mixture is put into the glasscarbon container, then in 900-1100 ℃ of following roasting 4 hours.Then, container is slowly cooled off also discharging.Soak molten alkynes with deionized water, be divided into mean particle size and be 5 microns finestructure thing.The structure of the complex chemical compound that makes is corresponding to formula Y
1.95Eu
0.1(VO
4)
2
Embodiment 4
100.0 gram lanthanum trioxides and 5.7 gram europium sesquioxides are mixed, 48.13 gram ammonium phosphate and 19.96 gram boric acid are added in the mixture.Mixture is put into the galsscarbon container, then 900-1100 ℃ of following roasting 4 hours.Then, container is slowly cooled off discharging.Handle molten alkynes with deionized water, be divided into mean particle size and be 4 microns finestructure thing.The structure of complex chemical compound is corresponding to formula Y
1.9Eu
0.1(BO
3) (PO
4).
Embodiment 5
As embodiment 4, except raw mix contains 100.0 gram yttrium oxide and 8.28 gram europium sesquioxides, 69.5 gram ammonium phosphate and 28.8 gram boric acid.The structure of the compound that makes is corresponding to formula Y
1.9Eu
0.1(BO
3) (PO
4).
Embodiment 6
100.0 gram yttrium oxide and 4.0 gram europium sesquioxides are mixed.Restraining vanadate and 40.6 gram ammonium phosphate and 5.6 gram boric acid with 63.8 is added in the mixture that makes.Mixture is put into the galsscarbon container, then 1200-1250 ℃ of following roasting 4 hours.Then, container is slowly cooled off discharging.Handle molten alkynes with deionized water, be divided into mean particle size and be 4 microns finestructure thing.The structure of complex chemical compound is corresponding to formula Y
1.95Eu
0.05(VO
4)
1.2(PO
4)
0.6(BO
3)
0.2
Embodiment 7
As embodiment 6, except raw mix contains 100.0 gram yttrium oxide and 8.2 gram europium sesquioxides, 54.5 gram vanadate, 48.6 gram ammonium phosphate and 8.6 gram boric acid.The structure of complex chemical compound is corresponding to formula Y
1.9Eu
0.1(VO
4)
1.0(PO
4)
0.7(BO
3)
0.3
Embodiment 8
100.0 gram yttrium oxide and 8.2 gram europium sesquioxides are mixed, 108.1 gram Tungsten oxide 99.999s and 28.8 gram boric acid are added in this mixture.Mixture is put into the galsscarbon container, then 900-1100 ℃ of following roasting 4 hours.Then, container is slowly cooled off discharging.Soak molten alkynes with deionized water, be divided into mean particle size and be 4 microns finestructure thing.The structure of complex chemical compound is corresponding to formula Y
1.9Eu
0.1(BO
2)
2(WO
4)
2
Embodiment 9
As embodiment 8,, raw mix replaces Tungsten oxide 99.999 except containing 67.1 gram molybdenum oxides.The structure of complex chemical compound is corresponding to formula Y
1.9Eu
0.1(BO
2)
2(MoO
4)
2
Embodiment 10
26.1 gram nitrate of baryta, 65.2 gram gadolinium sesquioxides, 7.0 gram europium sesquioxides, 43.2 gram molybdenum oxides are mixed.The mixture that obtains is put into the container that galsscarbon makes, then 600 ℃ of following roastings 2 hours, again 1100 ℃ of following roastings 2 hours.Container is slowly cooled off discharging.Soak molten alkynes with deionized water, be divided into mean particle size and be 5 microns finestructure thing.The structure of the complex chemical compound that makes is for answering formula Gd
1.8Eu
0.2(MoO
4)
4
Embodiment 11
With 23.0 gram yttrium oxide and 3.5 gram europium sesquioxides and 0.9 gram Sodium Fluoride mixing.The mixture that obtains is put into the alundum container, then 1100-1200 ℃ of following roasting 4 hours.Then, container is slowly cooled off discharging.Soak molten alkynes with deionized water, be divided into mean particle size and be 4 microns finestructure thing.The structure of the complex chemical compound that makes is corresponding to formula Y
1.9Eu
0.1OF.
Embodiment 12
As embodiment 2,, raw mix replaces europium sesquioxide except containing 10.0 gram Samarium trioxides.The structure of the complex chemical compound that makes is corresponding to formula Y
1.9Sm
0.1O
2S
1
Embodiment 13
As embodiment 2,, raw material contains 10.0 gram terbium sesquioxides replacement europium sesquioxides except mixing.The structure of the complex chemical compound that makes is corresponding to formula Y
1.9Tb
0.1O
2S
1
Embodiment 14
As embodiment 2,, raw mix replaces europium sesquioxide except containing 10.0 gram gadolinium sesquioxides.The structure of the complex chemical compound that makes is corresponding to formula Y
1.9Gd
0.1O
2S
1
Embodiment 15
As embodiment 2, except raw mix contains 32.6 gram lanthanums, 4.0 gram europium sesquioxides, 15.0 gram elementary sulfurs, 50.0 gram yellow soda ash and 1.3 gram lithium fluoride.The structure of the complex chemical compound that makes is corresponding to La
1.9Eu
0.1O
2S
1
Embodiment 16
As embodiment 4,, raw mix replaces europium sesquioxide except containing 5.6 gram Samarium trioxides.The structure of the complex chemical compound that makes is corresponding to formula La
1.9Sm
0.1(BO
3) (PO
4).
Embodiment 17
As embodiment 4,, raw mix replaces europium sesquioxide except containing 5.5 gram terbium sesquioxides.The structure of the complex chemical compound that makes is corresponding to formula La
1.9Tb
0.1(BO
3) (PO
4).
As embodiment 18-19 explanation, in water-pure medium, under 80-90 ℃, make the coordination compound of europium, samarium, terbium and the gadolinium of proposition by method with corresponding bronsted lowry acids and bases bronsted lowry treatment of nitric acid salt.
Embodiment 18
With heating 4.46 gram europium nitrates (III) are dissolved in 50 milliliters of ethanol.With the gram of 8.89 in 10 milliliters of ethanol thenoyltrifluoroacetone, then the gram of 8.44 in 15 milliliters of ethanol vulkacit D is added in the solution that obtains.With the solution cooling, filter out settling.Filtrate placement is freely evaporated.Amorphous-the crystallisate that makes has formula (DPhG) H[Eu (TTA)
4] structure.
Embodiment 19
4.46 gram europium nitrates (III) are dissolved in 50 milliliters of hot water.3.4 gram 1.10-phenanthroline in 10 milliliters of ethanol are added in the solution that makes.Deposit the crystallization deposition thing immediately.With the solution cooling, on the sintered glass film, filter out settling, use cold water washing, then with ethanol and ether washing.The structure of surplus compound is corresponding to formula [Eu (NO
3)
3(Phen)
2].
Embodiment 1-17 explanation can be used for complex chemical compound synthetic of commercial production.
Production contains the method for the light-converting material of matrix and active additive, its mesostroma is extruded into film or plate, or make by thermoplastic polymer or soluble polymer, be similar to disclosed preparation polymkeric substance in CH667463, GB2158833, the method for film or sheet.
Embodiment 20
In order to produce light-converting material, it is Y that preparation contains 99.8 kilograms of particle polyethylene, 0.1 kilogram of natural phosphatic rock and 0.1 kilogram of structural formula
1.9Eu
0.1(VO
4)
1.5(PO
4)
0.5The composition of complex chemical compound (mean particle size be 4 microns Powdered) generate component as matrix.Said composition is put into mixing tank, fully stir and be extruded into the film of 100-150 micron then.
The material that makes contains matrix and the natural phosphatic rock of active additive-0.1% (weight) and the described yttrium of 0.1% (weight)-europium vanadate-phosphoric acid salt.Active additive is disperseed with matrix, be extruded into film then.
The optical property of the material that makes is listed the quantum yield of the sunlight conversion of showing the 1:280-400 nanometer range in up to 85%, and the transmittance of 580-750 nanometer range is 82%, and luminosity stability was above 650 days.
The material of this transparent film form can be used for covering the greenhouse.
Embodiment 21-35 lists table 1 in.
Table 1The character that resembles the light-converting material that makes disclosed in embodiment 20 is described, wherein the complex chemical compound of the different structures of different amounts and the different natural and/or synthetic phosphatic rock of measuring are used as active additive.The character of the material of producing and similarity (last column in the table 1 of Comparative Examples, embodiment 36) relatively find out, under identical conversion intensity (stability of photoluminescence), the light transfer capability that this material can convert UV-light to red ray spectrum scope keeps reaching 650 days.
Embodiment 37-45 lists table 2 in.
Table 2The character of the light-converting material that is extruded into film is described, as described in embodiment 20, wherein different polymkeric substance generates agent as matrix, and the natural and/or synthetic phosphatic rock of the complex chemical compound of the different structure of different quantities and coordination compound and different quantities is as active additive.
As shown in table 2, the character that generates the polymkeric substance of agent as the matrix of producing this material keeps the time of light transfer capability not have influence to the material that is proposed.
And, found natural and/or synthetic phosphatic rock is added in the active additive and can strengthen light-converting material.For example, contain the particularly matrix made of polyethylene of film, as in embodiment 20, describing, and respectively contain 0.075% (weight) natural with synthetic phosphatic rock as active additive with contain 0.1% (weight) Y
1.95Eu
0.05O
2S is as complex chemical compound (embodiment 26) or contain synthetic phosphatic rock and 0.1% (weight) Y of 0.15% (weight)
1.95Eu
0.05O
2Its tensile strength of material of S (embodiment 34) is higher by 10% than Comparative Examples, and the slit extensibility of material is high 2 times.
Compare with Comparative Examples, the heat-proof quality matter of these materials improves.The Hu Wai soil moisture and use the difference between the soil moisture in the greenhouse that contains the additive material protection to be 2-5 ℃ for example, and when material protection that the greenhouse is described with embodiment 26 and 34, the difference of these temperature reaches 7-8 ℃.
Embodiment 46-48 lists table 3 in.
Table 3List that silicate (embodiment 46,47,48) makes, the character of the tabular light-converting material that polymethacrylate (embodiment 47), polycarbonate glass (embodiment 46) are made, its surface-coated have and contain active additive and be distributed in wherein clear coat composition.The material that embodiment 46-48 makes kept its light conversion character in 700 days.
Embodiment 49
To contain polypropylene non-woven fabric as matrix and the light-converting material that contains active additive in order producing, to use 0.1 kilogram of formula Y
1.9Eu
0.1O
2S
1Complex chemical compound, 0.1 kilogram of synthesizing hydroxylapatite and 100.0 kilograms of polypropylene GRANULES.Make this material with traditional method.The material that makes kept its light conversion character in 600 days.
Embodiment 50
To contain the light-converting material of cotton fiber cloth in order producing, to use solubility urethane and 0.03 kilogram of synthetic fluoridated apatite and 0.03 kilogram of formula La as matrix
1.9Eu
0.1(VO
4) (PO
4) 9.94 kilograms of cottons of impregnation mixture of complex chemical compound.This material kept its light transfer capability in 600 days.
Embodiment 51
To contain the textile-like light-converting material of polypropylene in order producing, to use the particle of 96.5 kilograms of this polymkeric substance, with them and active additive (0.2 kilogram of natural phosphatic rock and 0.3 kilogram of formula Y as matrix
1.9Eu
0.1O
2S
1Complex chemical compound) mix.Table 1 is made the optical property of the light-converting material of film
Table 1 (continuing)
Table 2 uses the optical property of the light-converting material of different polymkeric substance
Table 2 (continuing)
The component of table 3 clear coat composition and based on their optical property of light-converting material
| Embodiment | Matrix generates component (polyethylene), % (weight) | Active additive, % (weight) | The ultraviolet absorption scope, nanometer | The photo-quantum efficiency of conversion, % | The transmittance of the polymkeric substance that covers in the 580-700 nanometers, % | The stability of luminosity under the sunlight ray, day |
| 20 | 99.8 | Natural phosphatic rock-0.1 Y 1.95Eu 0.1(VO 4) 1..5(PO 4) 0.5-0.1 | ?280-400 | Up to 85 | 82 | 650 |
| 21 | 99.6 | Natural phosphatic rock-0.05 Gd 1.9Eu 0.1(VO 4) 1.2(PO 4) 0.8-0.35 | ?280-400 | Up to 86 | 84 | 650 |
| 22 | 99.7 | Natural phosphatic rock-0.1 La 1.9Eu 0.1(VO 4)(PO 4)-0.2 | ?280-400 | Up to 82 | 83 | 650 |
| 23 | 99.5 | Natural phosphatic rock-0.2 Y 1.95Eu 0.1(VO 4) 2-0.3 | ?280-400 | Up to 82 | 82 | 600 |
| 24 | 99.8 | Natural phosphatic rock-0.7 Y 1.9Eu 0.1(BO 3)(PO 4)-0.7 | ?280-400 | Up to 83 | 83 | 650 |
| 25 | 99.89 | Natural phosphatic rock-0.01 Y 1.9Eu 0.1O 2S-0.10 | ?280-400 | 81 | 80 | 650 |
| 26 | 99.75 | Every kind of phosphatic rock (natural and synthetic) is 0.075 Y 1.95Eu 0.05O 2S-0.10 | ?280-400 | 83 | 83 | 650 |
| 27 | 99.7 | Every kind of phosphatic rock (natural and synthetic) is 0.1 Y 1.9Eu 0.1(BO 2) 2(WO 4) 2-0.1 | ?280-400 | Up to 75 | 74 | 650 |
| 28 | 99.8 | Synthetic phosphatic rock is 0.1 Y 1.95Eu 0.1(VO 4) 1.5(PO 4) 0.5-0.1 | ?280-400 | Up to 85 | 85 | 650 |
| Embodiment | Matrix generates component (polyethylene), % (weight) | Active additive, % (weight) | The ultraviolet absorption scope, nanometer | The photo-quantum efficiency of conversion, % | The transmittance of the polymkeric substance that covers in the 580-700 nanometers, % | The stability of luminosity under the sunlight ray, day |
| 29 | 99.6 | Synthetic phosphatic rock-0.05 Gd 1.9Eu 0.1(VO 4) 1..2(PO 4) 0.8- 0.35 | ?280-400 | Up to 86 | 86 | 650 |
| 30 | 99.7 | Synthetic phosphatic rock-0.1 La 1.9Eu 0.1(VO 4)(PO 4)-0.2 | ?280-400 | Up to 82 | 84 | 650 |
| 31 | 99.5 | Synthetic phosphatic rock-0.2 Y 1.95Eu 0.1(VO 4) 2-0.3 | ?280-400 | Up to 82 | 85 | 600 |
| 32 | 98.6 | Synthetic phosphatic rock-0.7 Y 1.9Eu 0.1(BO 3)(PO 4)-0.7 | ?280-400 | Up to 83 | 81 | 650 |
| 33 | 99.89 | Synthetic phosphatic rock-0.01 Y 1.9Eu 0.1O 2S-0.10 | ?280-400 | 82 | 83 | 650 |
| 34 | 99.75 | Synthetic phosphatic rock-0.15 Y 1.95Eu 0.05O 2S-0.10 | ?280-400 | 83 | 84 | 650 |
| 35 | 99.7 | Synthetic phosphatic rock-0.2 Y 1.9Eu 0.1(BO 2) 2(WO 4) 2-0.1 | ?280-400 | Up to 75 | 79 | 650 |
| 36 | Known materials, RU2059999, polyethylene-99.5 | Synthetic phosphatic rock La 1.98Eu 0.02OBr-0.5 | ?280-420 | Up to 86 | 82 | 300 |
| Embodiment | Polymkeric substance, % (weight) | Active additive, % (weight) | The numerical value of absorbed UV-light in the 300-400 nanometer range, % | Absorb the transforming numerical of UV-light, % | The transmittance of the polymkeric substance that covers in the 580-700 nanometers, % | The stability of luminosity under the sunlight ray, day |
| 37 | Polyethylene 99.35 | Natural phosphatic rock-0.45 Y 1.9Eu 0.1(VO 4) 1.5(PO 4) 0.5-0.15 Y 1.9Sm 0.1(VO 4) 1.5(PO 4) 0.5-0.05 | 78 | 74 | 73 | Up to 650 |
| 38 | Polyethylene 99.79 | Natural phosphatic rock-0.1 Y 1.9Eu 0.1(VO 4) 1.2(PO 4) 0.8-0.1 Y 1.9Tb 0.1(VO 4) 1.2(PO 4) 0.8-0.01 | 81 | 72 | 74 | Up to 650 |
| 39 | The multipolymer 4%-99.84 vinyl acetate of ethene and vinyl acetate between to for plastic | Natural phosphatic rock-0.10 Y 1.9Eu 0.1(VO 4) 1.2(PO 4) 0.6(BO 3) 0.2-0.05 ?Eu(TTA) 3(Phen)-0.01 | 81 | 78 | 73 | Up to 650 |
| 40 | Polyethylene terephthalate 99.80 | Natural phosphatic rock-0.05 Y 1.9Eu 0.1(BO 3)(PO 4)-0.05 ?Eu 2(Ter) 3(Phen) 2-0.1 | 78 | 76 | 77 | Up to 650 |
| Embodiment | Polymkeric substance, % (weight) | Active additive, % (weight) | The numerical value of absorbed UV-light in the 300-400 nanometer range, % | Absorb the transforming numerical of UV-light, % | The transmittance of the polymkeric substance that covers in the 580-700 nanometers, % | The stability of luminosity under the sunlight ray, day |
| 41 | Polyethylene 99.35 | Synthetic phosphatic rock-0.45 Y 1.9Eu 0.1(VO 4) 1.5(PO 4) 0.5-0.15 Y 1.9Sm 0.1(VO 4) 1.5(PO 4) 0.5-0.05 | Up to 82 | 73 | 77 | Up to 650 |
| 42 | Polyethylene 99.79 | Synthetic phosphatic rock-0.1 Y 1.9Eu 0.1(VO 4) 1.2(PO 4) 0.8-0.1 Y 1.9Tb 0.1(VO 4) 1.2(PO 4) 0.8-0.01 | Up to 85 | 72 | 74 | Up to 650 |
| 43 | The multipolymer 4%-99.84 vinyl acetate of ethene and vinyl acetate between to for plastic | Synthetic phosphatic rock-0.10 Y 1.9Eu 0.1(VO 4) 1.2(PO 4) 0.6(BO 3) 0.2-0.05 (DPhG)H[Eu(TTA 4]-0.01 | Up to 83 | 80 | 74 | Up to 650 |
| 44 | Polyethylene terephthalate 99.80 | Synthetic phosphatic rock-0.05 Y 1.9Eu 0.1(BO 3)(PO 4)-0.05 ?Eu 2(Ter) 3(Phen) 2-0.1 | Up to 81 | 79 | 79 | Up to 650 |
| 45 | Polymethylmethacrylate 99.55 | Synthetic phosphatic rock-0.3 La 0.95Eu 0.05O 2S-0.1 ?Eu(TTA) 3(Phen)-0.05 | 78 | 74 | 73 | Up to 650 |
| Embodiment | The clear coat composition component | Matrix, thickness, nanometer | At the numerical value of 220-400 nanometers ultraviolet absorption, % | The numerical value of UV-light conversion, % | Transmittance at 580-700 nanometer range material |
| 46 | Acrylic acid or the like varnish-97.6 natural phosphatic rock-0.2 Y 1.9Eu 0.1(VO 4) 1.0(PO 4) 0.7(BO 3) 0. 3-2.0 (DPhG)H[Eu(TTA) 4]-0.2 | 4 millimeters polycarbonate glass of silicate glass, 2 millimeters | 80 83 | 45-50 80 | 71 73 |
| 47 | Epoxy resin varnish-99.5 natural phosphatic rock-0.4 Y 1.9Eu 0.1O 2S-0.4 (DPhG)H[Eu(HFAA) 4]-0.1 | Silicate glass, 4 millimeters polymethylmethacrylates, 2 millimeters | 85 85 | 78 80 | 69 79 |
| 48 | 5% sodium silicate aqueous solution-95.5 natural phosphatic rock-4.0 Y 1.9Eu 0.1(VO 4) 1.2(PO 4) 0.8 | Silicate glass, 4 millimeters | 79 | 77 | 66 |
The composition that makes is put into mixing tank, fully stir, then mixture is extruded into film, it is cut into linear fiber.Then the linear fiber that makes is come production textile-like light-converting material with traditional method.The material that makes kept its light conversion character in 650 days.
Embodiment 52
To contain the tabular light-converting material of borate-silicate glass in order producing, to use 98.0 kilograms of compositions that are used to produce silicate glass, 0.3 kilogram of natural phosphatic rock and synthetic phosphatic rock (1: 2) and 1.7 kilograms of formula Y as matrix
1.9Eu
0.1(BO
3) (PO
4) mixture of complex chemical compound is added in the composition.
The mixture that makes is placed in the mixing tank, fully stirs, be heated to 1000 ℃ then.Make sheet glass with usual method then.The material that makes kept its light conversion character in 700 days.
The light-converting material of the light transmissive films form that proposes is used for cultivating processes such as tomato, cucumber, capsicum, trailing plants Portugal, Radix Dauci Sativae and protects the greenhouse at different climatic zones.
Embodiment 53
This embodiment lists table 4 in, and its expression contains to some extent the result of mary bush growth in the greenhouse of different films protections of the light-converting material (as describing) that proposes in embodiment 20.
The normal polyethylene film that does not have the light conversion character is also as the test film.
Embodiment 54
This embodiment lists table 5 in, and table 5 explanation contains the result of radish growth in the greenhouse of different films protections of light-converting material (as describing) in embodiment 20.
The normal polyethylene film that does not have the light conversion character is as the test film.The productivity of mary bush growth in the greenhouse of the different polyethylene film protections of table 4
The productivity of radish growth in the greenhouse of the different polyethylene film protections of table 5
| Experiment | Plant gross weight gram | Ye Chongke | Branch is gram heavily | Root always restrains | Number of sheets amount sheet |
| Field | 32.1±2.5 | 32.0±1.3 | 15.3±0.5 | 4.8±0.1 | 6.0±0.3 |
| Experimental film | 40.8±2.1 | 22.0±1.0 | 15.8±0.3 | 3.0±0.04 | 40.4±2.3 |
| Light conversion film | 102.9±4.6 | 61.0±3.5 | 36.2±1.5 | 5.6±0.1 | 92.0±3.5 |
| Experiment | Number of sheets amount sheet | Ye Chongke | Radish heavily restrains | High centimetre of plant |
| Field | 8.3±0.3 | 34.1±0.8 | 34.4±1.1 | 29.0±2.1 |
| Experimental film | 7.54±0.2 | 35.8±0.9 | 40.9±1.5 | ?30.5±2.3 |
| Light conversion film | 6.0±0.2 | 43.4±1.0 | 55.9±1.6 | 34.4±0.5 |
List table 4 in, 5 experimental result shows, containing polyethylene film is that the greenhouse is effectively protected as the light-converting material of matrix.
Therefore, the light transformational effect of using the present invention ultraviolet ray might be converted to the material of red ray spectrum scope extends to 650 days, keeps its conversion intensity simultaneously.
The present invention also makes the quantity that is applicable to the material of producing the product with light conversion character enlarge becomes possibility.In addition, contain the material of thermoplastic polymer as matrix owing to make, the present invention can improve the thermal protective matter of this material, and its intensity is increased.
Owing to contain the raising of polymeric film, might produce at least 4 microns film as the strength of materials of matrix.Therefore, this material not only can be used for the protection in greenhouse and narrow and small seedbed, and can be used for protecting the farm crop in the field.
The intensity that the invention enables the raising ultraviolet ray to convert cyan and blue coloured light spectral limit to becomes possibility, and according to the data before us, it makes the productivity of plant improve 5% at least.
Industrial usability
The present invention can be used for agricultural with protection greenhouse and animal room; Be used for medicine, it can effectively prevent the mankind's sun calcination and/or promptly healing is provided, owing to reduce the ability of ultraviolet radiation dosage; With in optics industry, it can be used for producing light conversion cloth, for the manufacture of roof hood, cool fluffy, cloth; Be used for biotechnology, it can effectively be developed in ultraviolet ray and convert the equipment of cultivating microorganism and cell cultivation under the red color spectrum range to; Be used for engineering, it makes glass house and office building applicable to light conversion glass, greenhouse and animal room and manufacturing light conversion glass and automobile window.
Claims (23)
1. light-converting material that contains the active additive of a kind of matrix and a kind of light that UV-light can be converted to the orange-red light spectral limit, wherein active additive is a phosphatic rock, at least a formula M e
x mM
y 3R
z nComplex chemical compound or this complex chemical compound and at least a formula M e of europium (III)
x mM
y 3R
z nSamarium (III) or the mixture of the complex chemical compound of terbium (III) or gadolinium (III), in the formula, mx+3y=nz; Me
x m=Me
X ' M '+ Me
X " M "+ R
z n=R
Z ' N '+ R
Z " N "+ Mx=m ' x '+m " x "+ Nz=n ' z '+n " z "+ X 〉=1.0 〉=y 〉=0.01, wherein m and n are respectively Me or R ionic electric charge,
Me is the metal that is selected from yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, aluminium, bismuth, tin, titanium, manganese, calcium, barium, zinc, cadmium, sodium, potassium, rubidium, caesium,
M is the metal that is selected from europium, samarium, terbium, gadolinium,
R is element or its combination that is selected from oxygen, sulphur, fluorine, chlorine, bromine, phosphorus, boron, vanadium, molybdenum, tungsten, germanium,
Formula M e wherein
xM
yOGal or Me
xM
yO
2The complex chemical compound of Hal is solid solution processed products under 800-1200 ℃ in alkaline halide or chalcogenide medium of the oxide compound of Me and M,
Formula M e wherein
xM
yO
2S
1 ± 0.2Complex chemical compound be oxide compound processed products under 1200 ℃ in the sulphur medium of Me and M,
Formula M e wherein
xM
y(VO
4)
2Complex chemical compound be the oxide compound of solid phase Me and M and ammonium vanadate at 900-1100 ℃ of interactional product down,
Formula M e wherein
xM
y(BO
3)
Z '(PO
4)
Z "Complex chemical compound be the oxide compound of solid phase Me and M and boric acid and ammonium phosphate at 900-1100 ℃ of interactional product down,
Formula M e wherein
xM
y(VO
4)
Z '(PO
4)
Z "Complex chemical compound be the oxide compound of solid phase Me and M and vanadate and ammonium phosphate at 1000-1200 ℃ of interactional product down,
Formula M e wherein
xM
y(VO
4)
Z '(PO
4)
Z "(BO
3)
Z "Complex chemical compound be the oxide compound of solid phase Me and M and vanadate and ammonium phosphate and boric acid at 800-1100 ℃ of interactional product down,
Formula M e wherein
xM
y(BO
2)
Z '(WO
4)
Z "Or Me
xMY (BO
2)
Z '(MoO
4)
Z 'Complex chemical compound be that oxide compound, tungsten (molybdenum) and the boric acid of solid phase Me and M is at 1100-1200 ℃ of interactional product down.
2. according to the material of claim 1, wherein active additive distributes in the substrate or on the stromal surface.
3. according to the material of claim 1, wherein the quantity of active additive is at least 0.02% (weight) of this light conversion material.
4. according to the material of claim 1, its mesostroma is made into printing opacity.
5. according to the material of claim 1, wherein phosphatic rock is crystalline structure and finely divided natural or synthetic phosphatic rock, has formula Ca
10(PO
4)
6R
2, wherein R is F, Cl or OH, perhaps is the mixture of described compound in any ratio.
6. according to the material of claim 1, wherein said material also contains the coordination compound of at least a metal E, is selected from [E (TTA)
3(Phen)], [E (TTA)
3(TPhPO)
2], (DPhG) H[E (TTA)
4], (DPhG) H[E (HFAA)
4], [E (HFAA)
3(Phen)], [E (HFAA)
3(TPhPO)
2], (DPhG) H[E (AA)
4], [E (AA)
3(Phen)], [E (BB)
3(Phen)], [E (TFA)
3(Phen)], (DPhG) H[E (TFA)
4], [E (Capr)
3(Phen)], [E
2(Ter)
3(Phen)
2], [E (NO
3)
3(Phen)
2], E is the metal that is selected from europium, samarium, terbium, gadolinium, H is a hydrogen ion; TTA closes negatively charged ion for the thenoyltrifluoroacetone acid group; HFAA closes negatively charged ion for the hexafluoro acetylacetonate, and BB is that benzoylbenzoic acid closes negatively charged ion; AA is that acetylacetonate closes negatively charged ion; TFA closes negatively charged ion for the trifluoroacetone acid group; Capr is that caproic acid closes the root negatively charged ion; Ter closes negatively charged ion for terephthaldehyde's acid group; Phen is 1, the 10-phenanthroline; TPhPO is a triphenylphosphine oxide; DPhG is a vulkacit D.
7. according to the material of claim 6; wherein the coordination compound of metal E be the nitrate of europium (III), samarium (III), terbium (III) or gadolinium (III) by ketone or Acetyl Acetone or benzoyl phenylformic acid or trifluoroacetic acid or caproic acid or terephthalic acid and 1 in thenoyltrifluoroacetone or the hexafluoro ethanoyl, 10-phenanthroline or triphenylphosphine oxide or diphenylguanidine in water-pure medium at the 80-90 ℃ of product of handling down.
8. according to the material of claim 1, wherein matrix is extruded into film or plate or woven or non-woven fabrics or fiber.
9. material according to Claim 8, its mesostroma is made by thermoplastic polymer.
10. material according to Claim 8, its mesostroma is made by soluble polymer.
11. material according to Claim 8, its mesostroma is by the polyester that is selected from polymethylmethacrylate, poly-n-butyl methacrylate, polycarbonate, polyethylene terephthalate and derivative thereof, or by the polyolefine that is selected from polypropylene, polyvinyl chloride, polystyrene, polyethylene and derivative thereof, or by the polymeric amide or derivatives thereof, or the multipolymer of these polymkeric substance or mixture are made.
12. material according to Claim 8, its mesostroma is by the natural fiber that comprises cotton, silk, wool, hemp and blend thereof, or comprising polypropylene, acetic ester, caprone, nylon, polymeric amide, polyester, their multipolymer, their blend is made at interior synthon or natural fiber and natural and blends synthon.
13. material according to Claim 8, its mesostroma is made by the silicate glass of silicate glass or modification.
14. material according to Claim 8, its mesostroma is made by synthetic glass.
15. according to the material of claim 1, wherein it also contains varnish or tackiness agent.
16. according to the material of claim 15, wherein varnish or tackiness agent are silicone or polyester or polyepoxide or Resins, epoxy or their mixture.
17. a composition that is used to produce light-converting material contains matrix and generates agent and active additive, wherein active additive is phosphatic rock and at least a formula M e
x mM
y 3R
z nComplex chemical compound or this complex chemical compound and at least a formula M e of europium (III)
x mM
y 3R
z nSamarium (III) or the mixture of the complex chemical compound of terbium (III) or gadolinium (III), in the formula, mx+3y=nz; Me
x m=Me
X ' M '+ Me
X " M "+ R
z n=R
Z " N '+ R
Z N "+ Mx=m ' x '+m " x "+ Nz=n ' z '+n " z "+ X 〉=1.0 〉=y 〉=0.01, Me is the metal that is selected from yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, aluminium, bismuth, tin, titanium, manganese, calcium, barium, zinc, cadmium, sodium, potassium, rubidium, caesium, M is the metal that is selected from europium, samarium, terbium, gadolinium, R is element or its combination that is selected from oxygen, sulphur, fluorine, chlorine, bromine, phosphorus, boron, vanadium, molybdenum, tungsten, germanium, m and n are respectively Me or R ionic electric charge
Wherein complex chemical compound is wherein nz=3, R=formula Me of at least a compound
xM
yThe O of OGal, Gal, Gal=F, Cl, Br, perhaps wherein nz=6, R=formula Me
xM
yO
2The O of Hal, Hal, Hal=S or Se or formula Me
xM
yO
2S
1 ± 0.2O, S; Or nz=6 wherein, R=formula Me
xM
y(VO
4)
2VO
4Or R=formula Me wherein
xM
y(BO
3)
Z '(PO
4)
Z "BO
3, PO
4Perhaps R=formula Me wherein
xM
y(VO
4)
Z '(PO
4)
Z "VO
4, PO
4Perhaps R=formula Me wherein
xM
y(BO
2)
Z '(WO
4)
Z "Or Me
xM
y(BO
2)
Z '(MoO
4)
Z "BO
2, WO
4, MoO
4Or the mixture of these compounds,
Formula M e wherein
xM
yOGal or Me
xM
yO
2The complex chemical compound of Hal is solid solution processed products under 800-1200 ℃ in alkaline halide or chalcogenide medium of the oxide compound of Me and M,
Formula M e wherein
xM
yO
2S
1 ± 0.2Complex chemical compound be oxide compound processed products under 1200 ℃ in the sulphur medium of Me and M,
Formula M e wherein
xM
y(VO
4)
2Complex chemical compound be the oxide compound of solid phase Me and M and ammonium vanadate at 900-1100 ℃ of interactional product down,
Formula M e wherein
xM
y(BO
3)
Z '(PO
4)
Z "Complex chemical compound be the oxide compound of solid phase Me and M and boric acid and ammonium phosphate at 900-1100 ℃ of interactional product down,
Formula M e wherein
xM
y(VO
4)
Z '(PO
4)
Z "Complex chemical compound be the oxide compound of solid phase Me and M and vanadate and ammonium phosphate at 1000-1200 ℃ of interactional product down,
Formula M e wherein
xM
y(VO
4)
Z '(PO
4)
Z "(BO
3)
Z "Complex chemical compound be the oxide compound of solid phase Me and M and vanadate and ammonium phosphate and boric acid at 800-1100 ℃ of interactional product down,
Formula M e wherein
xM
y(BO
2)
Z '(WO
4)
Z "Or Me
xMY (BO
2)
Z '(MoO
4)
Z 'Complex chemical compound be that oxide compound, tungsten (molybdenum) and the boric acid of solid phase Me and M is at 1100-1200 ℃ of interactional product down, and matrix generation agent is thermoplastic polymer or soluble polymer, perhaps natural, synthetic or blended filamentary material, perhaps produce synthetic glass, the silicate compositions of silicate glass or modification or varnish/tackiness agent generates material, with the composition total weight is benchmark, and each component has following ratio (% (weight)):
Phosphatic rock 0.01-10.0
Complex chemical compound 0.01-10.0
Matrix generates the agent remainder.
18. according to the composition of claim 17, wherein it also contains the coordination compound of at least a metal E, it is selected from
[E (TTA)
3(Phen)], [E (TTA)
3(TPhPO)
2], (DPhG) H[E (TTA)
4], (DPhG) H[E (HFAA)
4], [E (HFAA)
3(Phen)], [E (HFAA)
3(TPhPO)
2], (DPhG) H[E (AA)
4], [E (AA)
3(Phen)], [E (BB)
3(Phen)], [E (TFA)
3(Phen)], (DPhG) H[E (TFA)
4], [E (Capr)
3(Phen)], [E
2(Ter)
3(Phen)
2], [E (NO
3)
3(Phen)
2], E is the metal that is selected from europium, samarium, terbium, gadolinium, H is a hydrogen ion; TTA closes negatively charged ion for the thenoyltrifluoroacetone acid group; HFAA closes negatively charged ion for the hexafluoro acetylacetonate; BB closes negatively charged ion for the benzoyl benzoate anion, and AA is that acetylacetonate closes negatively charged ion, and TFA closes negatively charged ion for the trifluoroacetone acid group; Capr closes negatively charged ion for the caproic acid root; Ter closes negatively charged ion for terephthaldehyde's acid group, and Phen is 1, the 10-phenanthroline; TPhPO is a triphenylphosphine oxide; DphG is a vulkacit D, is benchmark with the composition total weight, and each component has following ratio (% (weight)):
Phosphatic rock 0.01-10.0
Complex chemical compound 0.01-10.0
Coordination compound 0.01-10.0
Matrix generates the agent remainder
19. according to the composition of claim 17, it is the polymkeric substance that is selected from polymethylmethacrylate, poly-n-butyl methacrylate, polycarbonate, polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene, polyethylene, polymeric amide, their derivative, the multipolymer or the mixture of these polymkeric substance that its mesostroma generates agent.
20. according to the composition of claim 17, it is silicone or polyester or polyepoxide or Resins, epoxy or its mixture that its mesostroma generates agent.
21. according to the composition of claim 17, it is to be selected from natural fiber of silk, wool, cotton, hemp and composition thereof that its mesostroma generates agent.
22. according to the composition of claim 17, it is to be selected from synthon of viscose glue, acetic ester, polyester, polymeric amide, polyacrylamide and composition thereof that its mesostroma generates agent.
23. according to the composition of claim 17, its mesostroma generates agent for producing the composition of silicate glass or modified Portland glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182495 CN1125846C (en) | 1997-11-25 | 1997-11-25 | Light-converting material and composition for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182495 CN1125846C (en) | 1997-11-25 | 1997-11-25 | Light-converting material and composition for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1286716A CN1286716A (en) | 2001-03-07 |
| CN1125846C true CN1125846C (en) | 2003-10-29 |
Family
ID=5178541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97182495 Expired - Fee Related CN1125846C (en) | 1997-11-25 | 1997-11-25 | Light-converting material and composition for producing same |
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| Country | Link |
|---|---|
| CN (1) | CN1125846C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360609C (en) * | 2006-05-18 | 2008-01-09 | 吉林大学 | Method for preparing transparent hybridization material of polymetal oxygen cluster / polymer |
| CN102134486B (en) * | 2010-01-26 | 2014-01-29 | 海洋王照明科技股份有限公司 | Vacuum ultraviolet induced green emitting phosphor and preparation method thereof |
| CN102558205B (en) * | 2011-12-28 | 2014-09-03 | 阜阳师范学院 | Rare-earth complex and preparation method thereof and application of rare-earth complex serving as fluorescent sensor |
| CN102559179B (en) * | 2011-12-31 | 2014-11-05 | 浙江工业大学 | Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof |
| CN106637475B (en) * | 2016-11-23 | 2018-10-12 | 聊城大学 | A kind of preparation method using the curtain fiber of toxic gas in visible light and infrared light degradation room |
| CN106739320A (en) * | 2016-11-30 | 2017-05-31 | 庞倩桃 | Solar cell backboard |
| CN106830934B (en) * | 2017-01-23 | 2020-03-10 | 山东科技大学 | Microwave complex phase ceramic KxNayMoO4-TiO2And preparation method |
| CN111201912B (en) * | 2020-02-25 | 2021-03-02 | 浙江大学 | Method for increasing iron content in tomato fruits |
| CN113402744B (en) * | 2021-05-06 | 2022-11-08 | 甘肃颐年聚光科技有限责任公司 | Light conversion film capable of promoting plant growth and preparation method and application thereof |
-
1997
- 1997-11-25 CN CN 97182495 patent/CN1125846C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1286716A (en) | 2001-03-07 |
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